EP2000013B1 - Electrolytic method for filling holes and cavities with metals - Google Patents

Electrolytic method for filling holes and cavities with metals Download PDF

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Publication number
EP2000013B1
EP2000013B1 EP20070723814 EP07723814A EP2000013B1 EP 2000013 B1 EP2000013 B1 EP 2000013B1 EP 20070723814 EP20070723814 EP 20070723814 EP 07723814 A EP07723814 A EP 07723814A EP 2000013 B1 EP2000013 B1 EP 2000013B1
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Prior art keywords
holes
pulse
characterized
method according
work piece
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EP20070723814
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German (de)
French (fr)
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EP2000013A2 (en
Inventor
René WENZEL
Soungsoo Kim
Tafadzwa Magaya
Bert Reents
Bernd Roelfs
Markus Youkhanis
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Atotech Deutschland GmbH
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Atotech Deutschland GmbH
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Priority to EP20070723814 priority patent/EP2000013B1/en
Priority to PCT/EP2007/002872 priority patent/WO2007112971A2/en
Publication of EP2000013A2 publication Critical patent/EP2000013A2/en
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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/40Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42Plated through-holes or plated via connections
    • H05K3/423Plated through-holes or plated via connections characterised by electroplating method
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/38Electroplating: Baths therefor from solutions of copper
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18Electroplating using modulated, pulsed or reversing current
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/09Shape and layout
    • H05K2201/09209Shape and layout details of conductors
    • H05K2201/095Conductive through-holes or vias
    • H05K2201/09563Metal filled via
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/14Related to the order of processing steps
    • H05K2203/1476Same or similar kind of process performed in phases, e.g. coarse patterning followed by fine patterning
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/14Related to the order of processing steps
    • H05K2203/1492Periodical treatments, e.g. pulse plating of through-holes

Abstract

Disclosed is an electroplating method for filling cavities, through holes, pocket holes, or micropocket holes of a workpiece with metals. According to said method, the workpiece containing cavities, through holes, pocket holes, or micropocket holes is brought in contact with a metal deposition electrolyte, and a voltage is applied between the workpiece and at least one anode such that a current flow is fed to the workpiece. The inventive method is characterized in that the electrolyte encompasses a redox system.

Description

    Field of the invention
  • The present invention relates to an electrolytic method for filling wells, blind holes, microsyring holes and through holes in substrates with metals. The method is particularly suitable for filling blind holes in printed circuit boards with copper. However, it is also suitable to fill other wells with metals, especially copper. The method provides durable fillings even with small hole diameters, unwanted inclusions in the through hole can be hindered four. In addition, the filling has a very good thermal conductivity.
  • State of the art
  • The increasing miniaturization of electronic components simultaneously leads to an increase in integration density. For printed circuit boards, the trend towards miniaturization is reflected in the following design parameters: reduction of pad diameter and conductor width / conductor spacing as well as improved registration and an increase in the number of layers.
  • Circuit boards with these characteristics are generally referred to as high-density interconnects (HDI).
  • An important aspect of such HDI circuits in printed circuit board technology is the filling of through-holes and blind holes. Blind holes are also referred to as μ-blind vias (μ-BVs) from certain dimensions. Such μ-BVs or micro-blind holes serve to electrically connect at least two layers in printed circuit boards. Μ-BVs are referred to when the hole diameter of the vias is less than 0.15 mm (according to IPC) or the hole density is greater than 1000 vias / dm 3 . The term blind holes is used below as a generic term and includes μ-BVs.
  • The filling of the through holes or blind holes places considerable demands on the process control. It has to consider the different types of wells, meet the various requirements of the filling materials and take into account the downstream processing steps on a printed circuit board.
  • The present invention is primarily concerned with filling through holes in printed circuit boards that pass through the entire board (Plated Through Hole, PTH) and inside vias (buried vias) as well as blind holes.
  • The method is in principle suitable for filling through-holes and blind holes in various workpieces, in particular plate-shaped. Workpieces and plate-shaped electrical circuit carriers containing through holes or blind holes.
  • The closure of the through holes and blind holes is required inter alia to prevent the passage of solder on the components, to achieve a high integration density and to improve the electrical properties. In the case of multi-layer printed circuit boards, inclusions may occur during lamination of the next build-up position (due to air, solvents, etc.) in the holes, which lead to bulges during subsequent thermal stresses and consequently to cracks in the next layer.
  • Main requirements for filling materials for through holes Blind holes are therefore:
    • Solvent-free
    • Good adhesive properties to the sleeve and solder stop
    • Resistance to process chemicals in subsequent steps (for example galvanic metallization with nickel, gold or tin).
    • Resistance in hot air leveling processes.
  • Various methods for filling through-holes and blind holes are described in the prior art.
  • In the simplest case, the holes are filled with a specially set solder stop. Their advantage is that at high Integratiönsdichte no impairment in the resolution of the forcibly as a rivet head protruding through hole filler is given. A disadvantage, however, is the risk of solvent inclusions, which can evaporate abruptly in subsequent process steps such as tinning and thereby tear the cover.
  • However, this method is unsuitable for closing through holes in inner layers. Here, the inner layers must be completely closed to prevent inclusions. For this process, the plugging is widespread, because this method makes it possible to produce an inner layer by a coppering of the filled through-hole, which can be structured without restriction.
  • The filler material used is various dielectrics, such as, for example, resin-coated copper foils (RCC) or photodielectric liquid or dry films.
  • The EP 0645 950 B1 describes a method for producing multilayer circuit substrates. As the through-hole filler, there are used thermosetting resins selected from the group consisting of phenolic resin and epoxy resin. Further, at least one metal powder selected from the group consisting of silver, nickel, copper and an alloy thereof is added to the resin as a conductive substance.
  • The plugging usually takes place after the circuit board has been drilled and the holes have finally been metallized, but before the structuring. After filling the vias and hardening the plugging paste, it is mechanically leveled, as it has a light rivet head through the filling process. Often, then, a metallization of the paste with copper, so that a continuous copper layer is produced as Abschlu߬ layer. For simplicity, the following steps are required.
    • Drill
    • Metallizing the sleeve
    • plugging
    • Brushing, grinding
    • Metallizing the plugging paste
    • Applying the next installation position.
  • The EP 1 194 023 A1 describes the fabrication of HDI printed circuit boards by filling through holes with conductive pastes, wherein the curing of the paste can occur simultaneously with the pressing of the base material, thereby creating an electrical contact of internal layers.
  • Other methods fill the vias and blind holes by metallization with copper.
  • The EP 1 264 918 A1 describes a process for the electrolytic deposition of copper, which is particularly suitable for filling μ-blind vias. The use of inert anodes in a dummy plating phase here leads to the maintenance and improvement of the filling capacity of the electrolyte.
  • According to EP 1 219 729 A1 Chemicals such as formaldehyde as well as oxidants are used to extend the life of the metallization bath, which is particularly suitable for filling μ-blind vias. Sulfur-containing substances containing sulfonic acid groups and thiol-reactive compounds are used as additives.
  • The DE 103 25 101 describes a method for filling μ-blind vias characterized by the following steps:
  1. (i) Use of a bath electrolyte for plating with metallic coatings comprising metal salts, acids and organic additives, the bath comprising an inorganic matrix comprising 15-60 g / l copper, 40-300 g / l sulfuric acid and 20-150 mg / l chloride and the organic additives include brighteners, wetting agents and other additives selected from polyamides, polyamines, lactam alkoxylates, thioureas, oligomeric and polymeric phenazonium derivatives and aminotriphenylmethane dyes,
  2. (ii) operating the bath with direct current at a current density of 0.5-2.5 A / dm 2 or current pots with an effective current density of 0.5-10 A / dm 2 ;
  3. (iii) removing part of the electrolyte from the plating bath,
  4. (iv) adding an oxidizing agent to the removed part,
  5. (v) optionally irradiating the removed electrolyte with UV light and
  6. (vi) returning the removed part to the plating bath and replenishing the organic additives destroyed by the oxidation treatment.
  • In the conventional metallization of holes, for example, in printed circuit boards, an approximately equal dispersion at the ends of the holes and their center is first observed. During the metal deposition the aspect ratio changes and in the borehole the scattering becomes smaller. This leads to increased metal deposition at the borehole ends, which grow before the inner space is metallized filling. In The holes then leave behind unwanted inclusions, in particular residues of the metallizing bath.
  • In addition, the problem arises that not only are the holes metallized, but also the substrate surface is metallized. This is undesirable and affects the process considerably.
  • Summary of the invention
  • The present invention is therefore based on the object of providing a method for filling depressions, through holes and blind holes or microsack holes, in which the metal deposition preferably takes place in the holes and not on the substrate surface.
  • This object can surprisingly be achieved by using a redox system (ie a Fe 2 + / 3 + system) in the metallization bath, whereby the metal deposition is surprisingly preferably carried out in the depressions, through holes and blind holes or microsack holes.
  • In printed circuit board technology, a preferred field of application of the present invention, these holes are filled with metal.
  • Description of the drawings
  • Figures 1a and 1b show the formation of a constriction by preferential copper plating in the middle of a through hole in a printed circuit board.
  • The Figure 2 shows a filled through-hole after forming a constriction in the center of the hole and then filling it.
  • The Figure 3 shows a pulse reversal current diagram with phase shift and pulse pause.
  • The Figure 4 shows a schematic representation of an apparatus which is suitable for the treatment of workpieces in the dipping process.
  • Figures 5a and 5b show the deposition of copper in a blind hole and on the surface of a printed circuit board from a bath with different Fe (III) contents.
  • Description of preferred embodiments of the invention
  • In a preferred embodiment of the present invention, the method is used to fill through holes in printed circuit boards having a maximum height of 3.5 mm, a preferred height of 0.025-1 mm, and a particularly preferred height of 0.05-0.5 mm, as well as a Diameter of at most 1000 .mu.m, preferably 30-300 .mu.m, and more preferably from 60-150 .mu.m.
  • In the method according to the invention for filling through holes of a workpiece with metals, in principle any suitable electrolyte for the electrodeposition can be used, such as electrolytes for depositing gold, tin, nickel or alloys thereof. Preferably, copper is used as the metal. The electrolyte may, for example, the above-mentioned composition according to DE 103 25 101 and additionally the Fe (II) / Fe (III) redox system.
  • It has been found that electrolytes used to deposit copper having the following composition give the best results:
    • Copper can be added to the electrolyte as a copper sulfate pentahydrate (CuSO 4 .5H 2 O) or as a copper sulphate solution. The working range is between 15 - 75 g / l copper.
  • Sulfuric acid (H 2 SO 4 ) is added as a 50-96% solution. The working range is between 20-400 g / l, preferably 50-300 g / l.
  • Chloride is added as sodium chloride (NaCl) or hydrochloric acid solution (HCl). The working range of chloride here is between 20-200 mg / l, preferably 30-60 mg / l.
  • Furthermore, the electrolyte preferably comprises brighteners, levelers and wetting agents as organic additives.
  • Wetting agents are usually oxygenated, high molecular weight compounds in concentrations of 0.005-20 g / l, preferably 0.01-5 g / l. Examples are given in Table 1: Table 1 wetting agent carboxymethylcellulose Nonylphenol polyglycol ether Octanediol-bis- (polyalkylene glycol ether) Octanolpolyalkylenglykolether Oleic acid polyglycol Polyethyleriglykol-polypropylene glycol copolymer) polyethylene glycol Polyethylene glycol dimethyl ether polypropylene glycol polyvinyl alcohol β-naphthol polyglycol ether Stearic acid potygtykötester Stearyl polyglykolether
  • As brighteners sulfur-containing substances are generally used, which are listed in Table 2: Table 2 sulfur compounds 3 (Benzothiazolyl-2-thio) -propylsulfonic acid, sodium salt 3-Mercaptopropane-1-sulfonic acid, sodium salt Ethylene dithiodipropyl sulfonic acid, sodium salt Bis- (p-sulphophenyl) -disulfide, disodium salt Bis (ω-sulfobutyl) disulfide, disodium salt Bis (ω-sulfohydroxypropyl) disulfide, disodium salt Bis (ω-sulfopropyl) disulfide, disodium salt Bis (ω-sulfopropyl) sulfide, disodium salt Methyl (ω-sulfopropyl) disulfide, disodium salt Methyl (ω-sulfopropyl) trisulfide, disodium salt O-ethyl-dithiocarbonic acid S (ω-sulfopropyl) ester, potassium salt thioglycolic Thiophosphoric acid O-ethyl bis (ω-sulfopropyl) ester, disodium salt Thiophosphoric tris (ω-sulfopropyl) ester, trisodium salt
  • As leveling agents, polymeric nitrogen compounds (eg polyamines or polyamides) or nitrogen-containing sulfur compounds, for example thiourea derivatives or lactam alkoxylates, can be used, as described in patent DE 38 36 521 C2 described, are used. The concentrations of the substances used are in a range of 0.1-100 ppm.
  • Furthermore, polymeric phenazonium derivatives described in the patent DE 41 26 502 C1 described are used. Other substances used to fill blind holes are dyes based on an aminotriphenylmethane structure such as malachite green, rosalinine or crystal violet.
  • For example, inert anodes can be used as anodes. Soluble anodes are possible in principle.
  • It has now been found that the use of a redox system (ie a Fe 2 + / 3 + system) surprisingly leads to the metal deposition preferably taking place in the recesses, through holes and blind holes.
  • Concentrations: Fe (II): at least 1 g / l, preferably 2-25 g / l.
  • Fe (III): 6-30 g / l, preferably 6-15, more preferably 6-9 g / l, and particularly preferably 6-8 g / l.
  • A typical arrangement that is suitable for treating the workpieces in the dipping process is in Figure 4 schematically shown in the container 1 is the plating solution 2, the compounds of the electrolytic reversible redox system contains (iron (II) - and iron (III) ions). The deposition solution can serve, for example, for copper plating and then contains the ingredients specified above. The workpieces 3, for example printed circuit boards, and the anodes 4, for example titanium oxide coated with iridium oxide, dip into the plating solution. The workpieces and the anodes are connected to the power source 5. Instead of a regulation of Current to the power source can also serin a voltage supply, with which the voltage between the workpieces and the anodes is controlled. The deposition solution is continuously fed by means not shown conveyors, such as pumps, to a second container 6.
  • In this separate container, the meta-ion generator through which the precipitation solution flows, the metal in the precipitation solution is replenished. In the metal ion generator, in the case of copper deposition, there are metallic copper parts, for example in the form of pieces, spheres or pellets. The copper parts dissolve under the action of the oxidized form of the redox compounds to copper ions. Due to the dissolution of the copper parts, the oxidized. Form of the redox system converted into the reduced form. The enriched with copper ions and the reduced form solution is returned to the first container by means of the pumps, not shown. The metallic copper used for the regeneration does not need to contain phosphorus, but phosphorus does not interfere either. By contrast, in conventional use of soluble copper anodes, the composition of the anode material is of great importance: in this case, the copper anodes must contain about 0.05% by weight of phosphorus. Such materials are expensive and the addition of phosphorus causes residues in the electrolytic cell to be removed by additional filtering.
  • Decisive is the sufficiently high concentration of Fe (III) ions, which has not previously been described in the prior art.
  • For acidic copper, DC and AC electrolytes, soluble anodes can also be used.
  • Furthermore, it has been found that metal filling, particularly in horizontal methods, provides particularly good results using a special type of metallization by means of a pulse reversal current. This special technique is characterized by a phase shift of 180 ° between the two pulse shapes generated by two separate pulse rectifiers. By means of the two rectifiers, the two sides of a printed circuit board can be metallized separately. Another special feature is the use of a periodically repeating pulse pause for both rectifiers, which is chosen so that at the same time the backward or reverse current pulse acts on the other side, see Figure 3 ,
  • Reverse pulse plating has been developed for the electrodeposition of copper, in particular, on high aspect ratio printed circuit boards and is known, for example, in US Pat DE 42 25 961 C2 and DE 27 39 427 A1 described. By using high current densities, improved surface distribution and dispersion in the through holes is achieved.
  • In the method according to the invention, the following parameters are preferably set:
    • The ratio of the duration of the at least one forward current pulse to the duration of the at least one reverse current pulse is set to at least 5, preferably to at least 15 and more preferably to at least 18. This ratio can be set to at most 100, and preferably at most 50. Most preferably, the ratio is adjusted to about 20.
  • The duration of the at least one forward current pulse can be set to at least 5 ms to 250 ms, preferably 20-240 ms and particularly preferably 80-160 ms.
  • The duration of the at least one reverse current pulse is set to at most 20 ms, preferably 1-10 ms, more preferably 1-8 ms and particularly preferably 4-5 ms.
  • The peak current density of the at least one forward current pulse on the workpiece is preferably set to a value of at most 15 A / dm 2 . Preferably, the peak current density of the at least one forward current pulse on the workpiece is about 1.5-8 A / dm 2 in horizontal methods, more preferably 7-8 A / dm 2 . In vertical methods, the most preferred peak current density of the windest one forward current pulse on the workpiece is a maximum of 2 A / dm 2 .
  • The peak current density of the at least one reverse current pulse on the workpiece is preferably set to a value of at most 60 A / dm 2 . The peak current density of the at least one reverse current pulse on the workpiece is preferably about 30-50 A / dm 2 , particularly preferably 30-40 A / dm 2 in horizontal methods. In vertical methods, the particularly preferred peak current density of the at least one forward current pulse at the workpiece is a maximum of 3 - 10 A / dm 2 .
  • The pulse pause is generally 0-8 ms depending on the reverse pulse parameter and the phase shift.
  • The phase shift is 0 ° -180 °, preferably 0 ° or 180 °.
  • A variant of the method for filling recesses, through holes and blind holes of a workpiece with metals comprises the following method steps:
    1. (i) contacting the workpiece containing via holes with a metal deposition electrolyte and applying a voltage between the workpiece and at least one anode to provide current flow to the workpiece, wherein the current flow is selected to be in accordance with illustration 1 a and b, a preferential deposition takes place in the middle of the through holes and as a result the through holes grow together completely or approximately completely;
    2. (ii) further contacting the workpiece with a metal deposition electrolyte and applying a voltage between the workpiece and at least one anode so as to provide current flow to the workpiece, wherein those obtained in step (i) are fully or nearly fully contained two halves divided through holes to the desired degree according to Figure 2 be filled up by the metal.
  • By applying the two-stage process according to the invention, a possibility is created for the first time to fill a through-hole with a pure metal layer. The filling methods described in the prior art use pastes - mostly conductive - because it was previously believed that the production of a compact metal layer is not possible with the required durability and the desired properties.
  • In a preferred embodiment of the present invention, the method comprises the following method steps:
    1. a. a first voltage is applied between a first side of the workpiece and at least a first anode so that a first pulse reversing current is applied to the first side of the workpiece, wherein in each cycle first pulse reversal current flow at least a first forward current pulse and at least a first reverse current pulse.
    2. b. a second voltage is applied between a second side of the workpiece and at least one second anode to provide a second pulse reversing current to the second side of the workpiece, wherein at least one second forward current pulse and at least a second reverse current pulse are included in each cycle of this second pulse reversing current flow.
    3. c. The workpiece is in contact with an electrolyte, wherein the redox system contains (Fe 2 + / 3 + - System).
  • Concentrations: Fe (II): at least 1 g / l, preferably 2-25 g / l.
  • Fe (III): 6-30 g / l, preferably 6-15, more preferably 6-9 g / l, and particularly preferably 6-8 g / l.
  • As far as this latter embodiment is concerned, the at least one first forward current pulse or the at least one first reverse current pulse can be offset from the at least one second forward current pulse or to the at least one second reverse current pulse. In a further preferred embodiment of the present invention, this offset between the first and second current pulses is about 180 °.
  • To further enhance dispersion, the current flow in each cycle may include two forward current pulses, with zero current interruption between the two forward current pulses and a reverse current pulse.
  • In the further course of the metallization process, at least one parameter of the pulse reversal current may be varied, this parameter selected being one of a group comprising the ratio of the duration of the forward current pulse to the duration of the reverse current pulse and the ratio of the peak current density of the forward current pulse to the peak current density of the reverse current pulse. In particular, it has proved advantageous to increase the ratio of the peak current density of the forward current pulse to the peak current density of the reverse current pulse during metallization of the workpiece and / or the ratio of the duration of the forward current pulse to the duration of the reverse current pulse reduce.
  • The invention is explained in more detail by the following example:
  • Embodiment 1
  • The Inpulse 2 modules used by Atotech Deutschland GmbH for the horizontal treatment of printed circuit boards (in which plates are transported for treatment in a horizontal path and in the horizontal transport plane) have a distance of 15 mm between the spray nozzle and the cathode (workpiece) and a distance of 8 mm between anode and cathode.
  • For the metallization, a printed circuit board of FR4 material, the dimensions 18 "x 24" = 457 mm x 610 mm and with a blind hole diameter of 100 microns and a depth of 70 microns used (Tables 2 and 3, each 3rd line from the top ), if not stated otherwise.
  • Before the metallization, the surface of the circuit board is first cleaned for 45 seconds with the cleaner Cuprapro CF from Atotech Germany GmbH and then treated with 5% sulfuric acid for 45 seconds.
  • The electrolytes used have the following composition. The metallization takes place in all cases at a temperature of 40 ° C.
    • Copper: 70 g / l
    • Sulfuric acid: 80 g / l
    • Chloride ions: 40 mg / l
    • Iron (II): 12 g / l
    • Iron (III): 2-8 g / l
    • Leveler Inpulse 2HF: 18ml / l; Brightener Inpulse 2: 12 ml / l
    • Inpulse levelers and brighteners are products of Atotech Deutschland GmbH.
  • In accordance with the above described general procedure for horizontal methods, the circuit board is treated for a period of time indicated in Tables 4 and 5 in an electrolytic plating bath with Inpulse 2HF and a pulse reversal flow method with the parameters shown in Table 3. A deposition of copper in the through holes is obtained as in Figure 5a shown.
  • In the second experiment, a similar circuit board in an electrolytic metallization bath with Inpulse 2HF copper and a pulse reversal flow method is treated with the parameters shown in Table 3, this time with a significantly lower Fe (III) content of 3 g / l instead 7 g / l. This gives a deposition of copper in the blind hole and on the surface according to Figure 5b , Table 3. Pulse parameters in metallization with copper attempt I forward / reverse I
    in A / dm 2
    Pulse parameter in ms
    Forward / reverse pulse
    Pulse break in ms Phase shift in ° copper
    g / l
    Fe (III)
    g / l
    sulfuric acid
    g / l
    10a 5/40 80/4 4 0 70 7 80 10b 5/40 80/4 4 0 70 3 80
  • Clearly visible is the lower deposition of copper in Figure 5a due to the higher concentration of iron (III) ions in the solution on the surface (lower layer thickness of copper) compared to Figure 5b , This difference is shown in Tables 4 and 5 for different blind hole dimensions (column Deposition Quantity): Table 4: Backfilling of blind holes by Inpulse 2HF method at low Fe (III) content (3 g / l) blind
    diameter
    blind
    depth
    deposition time deposition amount remaining
    deepening
    80 μm 60 μm 26 min. 20 μm <10 μm 100 μm 70 μm 30 min. 23 μm <10 μm 125 μm 70 μm 35 min. 27 μm <10 μm 100 μm 100 μm 41 min. 32 μm <10 μm
    blind
    diameter
    blind
    depth
    deposition time deposition amount remaining
    deepening
    80 μm. 60 μm 22 min. 12 μm <10 μm 100 μm 70 μm 27 min. 15 μm <10 μm 125 μm 70 μm 30 min. 17 μm <10 μm 100 μm 100 μm 36 min. 20 μm <10 μm
  • Claims (16)

    1. Galvanic method for filling cavities, through holes, blind holes or micro blind holes of a work piece with metals, comprising bringing into contact the work piece containing cavities, through holes, blind holes or micro blind holes with a metal deposition electrolyte and applying a voltage between the work piece and at least one anode such that a current flow is fed to the work piece, characterized in that the electrolyte contains a redox system, wherein the redox system is a Fe(II)/Fe(III) redox system and Fe(II) is contained in a concentration of at least 1 g/l and Fe(III) is contained in a concentration of 6-30 g/l.
    2. Method according to claim 1, characterized in that Fe(II) is contained in a concentration of 2-25 g/l and Fe(III) is contained in a concentration of 6-15 g/l.
    3. Method according to claim 2, characterized in that Fe(III) is contained in a concentration of 6-9 g/l.
    4. Method according to claim 1, characterized in that the electrolyte contains 15-75 g/l copper, 50-300 g/l H2SO4 and 20-200 mg/l chloride.
    5. Method according to any one of claims 1 to 3, characterized in that the Fe(III) content amounts to 6-8 g/l.
    6. Method according to claims 1 to 4, characterized in that the current flow in a first step (i) is selected such that a preferred deposition occurs in the center of the through holes and as a result the through holes grow together completely or almost completely, and in a further step (ii) further bringing into contact the work piece with a metal deposition electrolyte and applying a voltage between the work piece and at least one anode is carried out such that a current flow is fed to the work piece, wherein the through holes obtained according to step (i), which are completely or almost completely divided into two halves, are filled by the metal,
      wherein the current flow according to step (i) is a pulse reverse current and at least one forward current pulse and at least one reverse current pulse occurs in each current cycle and that the current flow according to step (ii) is either a pulse reverse current, a direct current or an alternating current, and wherein in step (i) the ratio of the duration of the at least one forward current pulse to the duration of the at least one reverse current pulse is adjusted to 5-75, the duration of the at least one forward current pulse is adjusted to 5-250 ms and the duration of the at least one reverse current pulse is adjusted to 20 ms at the most.
    7. Method according to claim 6, characterized in that the metallization steps (i) and (ii) are carried out in the same electrolyte.
    8. Method according to claim 6, characterized in that the ratio of the duration of the at least one forward current pulse to the duration of the at least one reverse current pulse is adjusted to about 20.
    9. Method according to claim 6, characterized in that the duration of the at least one reverse current pulse is adjusted to 1-10 ms.
    10. Method according to any one of claims 6 to 9, characterized in that the peak current density of the at least one forward current pulse at the work piece is preferably adjusted to 15 A/dm2 at the most, particularly preferred to 1.5-8 A/dm2 in horizontal methods and particularly preferred to 2 A/dm2 at the most in vertical methods.
    11. Method according to any one of claims 6 to 9, characterized in that the peak current density of the at least one reverse current pulse at the work piece is preferably adjusted to 60 A/dm2 at the most, particularly preferred to 30-50 A/dm2 in horizontal methods and particularly preferred to 3-10 A/dm2 in verticals methods.
    12. Method according to any one of claims 6 to 11, characterized in that a first voltage is applied between a first side of the work piece and at least one first anode such that a first pulse reverse current is fed to the first side of the work piece, wherein at least one first forward current pulse and at least one first reverse current pulse flow in each cycle of said first pulse reverse current,
      a second voltage is applied between a second side of the work piece and at least one second anode such that a second pulse reverse current is fed to the second side of the work piece, wherein at least one second forward current pulse and at least one second reverse current pulse flow in each cycle of said second pulse reverse current.
    13. Method according to claim 12, characterized in that the first current pulse is shifted with respect to the second current pulse by about 180°.
    14. Method according to any one of claims 1 to 13, characterized in that the holes have a maximum height of 3.5 mm, a preferred height of 0.025 mm - 1 mm and a particularly preferred height of 0.05 - 0.5 mm.
    15. Method according to any one of claims 1 to 13, characterized in that the holes have a diameter of 1000 µm at the most, preferably 30 µm - 300 µm and particularly preferred 60 µm - 150 µm.
    16. Method according to any one of claims 1 to 15, characterized in that the work piece is a circuit board or another electric circuit support in board form.
    EP20070723814 2006-03-30 2007-03-30 Electrolytic method for filling holes and cavities with metals Active EP2000013B1 (en)

    Priority Applications (3)

    Application Number Priority Date Filing Date Title
    EP06090045 2006-03-30
    EP20070723814 EP2000013B1 (en) 2006-03-30 2007-03-30 Electrolytic method for filling holes and cavities with metals
    PCT/EP2007/002872 WO2007112971A2 (en) 2006-03-30 2007-03-30 Electrolytic method for filling holes and cavities with metals

    Applications Claiming Priority (1)

    Application Number Priority Date Filing Date Title
    EP20070723814 EP2000013B1 (en) 2006-03-30 2007-03-30 Electrolytic method for filling holes and cavities with metals

    Publications (2)

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    EP2000013A2 EP2000013A2 (en) 2008-12-10
    EP2000013B1 true EP2000013B1 (en) 2010-10-13

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    EP (1) EP2000013B1 (en)
    JP (1) JP5073736B2 (en)
    KR (1) KR101335480B1 (en)
    CN (1) CN101416569B (en)
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    DE (1) DE502007005345D1 (en)
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    AT484943T (en) 2010-10-15
    US20090301889A1 (en) 2009-12-10
    EP2000013A2 (en) 2008-12-10
    JP2009531542A (en) 2009-09-03
    KR20090017492A (en) 2009-02-18
    DE502007005345D1 (en) 2010-11-25
    CN101416569B (en) 2011-04-06
    WO2007112971A3 (en) 2007-11-29
    JP5073736B2 (en) 2012-11-14
    KR101335480B1 (en) 2013-12-02
    WO2007112971A2 (en) 2007-10-11
    US8784634B2 (en) 2014-07-22
    CN101416569A (en) 2009-04-22

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